Ethylenically unsaturated monomer polymerization with silyl acyl peroxides and acyl peroxy polysiloxanes

ABSTRACT

There is described herein a copolymer formed by the polymerization of a) a polysiloxane of a silyl acylperoxy compound containing at least one of the following structures;   WHEREIN R&#39;&#39; is an alkylene, aralkylene or alkarylalkylene radical, R&#39;&#39;&#39;&#39; is an alkyl or aralkyl radical, Z is a monovalent hydrolyzable radical or monovalent organic radical bonded to the silicon atom by a carbon to silicon bond and wherein x is an integer from 0 to 3 inclusive, and provided that when x is greater than zero, the oxygen atom is in turn bonded to another silicon whereby to form a siloxane, wherein said siloxane and any remaining siloxane units in said siloxane composition are of the formula;

United States Patent 91 [451 Apr. 10, 1973 [54] ETHYLENICALLYUNSATURATED MONOMER POLYMERIZATION WITH SILYL ACYL PEROXIDES AND ACYLPEROXY POLYSILOXANES [75] Inventor: John R. Joy, Stevenson, Md.

[73] Assignee: Union Carbide Corporation, New

York, N.Y.

[22] Filed: Aug. 12, 1971 [2]] Appl. No.: 171,356

Related US. Application Data [62] Division of Ser. No. 82,817, Oct. 21,1970.

260/4482 N [51 Int. Cl. ..C08f 35/02 [58] Field of Search ..260/46.5 R,46.5 E,

260/465 Y, 46.5 G, 827, 77.5 R, 77.5 AP, 448.2 B, 448.2 N

[56] References Cited UNITED STATES PATENTS 2,963,501 12/1960Plueddemann ..260/448.2

Primary ExaminerDonald E. Czaja Assistant Examiner-Melvyn l. MarquisAttorneyPaul A. Rose, George A. Skoler and Aldo J. Cozzi 57 ABSTRACTThere is described herein a copolymer formed by the polymerization of a)a polysiloxane of a silyl acylperoxy compound containing at least one ofthe following structures;

wherein R is an alkylene, aralkylene or alkarylalkylene radical, R" isan alkyl or aralkyl radical, Z is a monovalent hydrolyzable radical ormonovalent organic radical bonded to the silicon atom by a carbon tosilicon bond and wherein x is an integer from O to 3 inclusive, andprovided that when x is greater than zero, the oxygen atom is in turnbonded to another silicon whereby to form a siloxane, wherein saidsiloxane and any remaining siloxane units in said siloxane compositionare of the formula;

w 4-wIZ (*5) r R N ooon" wherein Z, R, R" and y are as herein definedand w is l to 3 inclusive; y is 0 to l, and z is l or 2; with theproviso that when y is 0, the acyl carbonyl carbon is bonded to R, the Rhaving at least 2 sequential carbon atoms separating the acyl carbonylcarbon atom from the silicon atom; with the further proviso that when yis 1, z is l and the nitrogen atom is bonded to a carbon atom of R, theR having at least 3 sequential carbon atoms separating the nitrogen fromthe silicon atom, and b) an ethylenically unsaturated monomer.

wherein Z is Z or 10 Claims, No Drawings ETHYLENICALLY UNSATURATEDMONOMER POLYMERIZATION WITH SILYL ACYL PEROXIDES AND ACYL PEROXYPOLYSILOXANES This is a division of application Ser. No. 082,817 filedOct. 21, 1970.

This invention relates to silyl acyl peroxides in the form of silanes orsiloxanes. Specifically this invention relates to silyl acyl peroxidesin which the acyl carbonyl carbon atom is separated by at least 2sequential carbon atoms of an alkylene or aralkylene radical from thesilicon atom to which it is bonded. This invention also relates to silylcarbamyl peroxides in which an acyl peroxy carbonyl carbon atom isbonded to a nitrogen atom which in turn is separated by at least 3sequential carbon atoms of an alkylene or aralkylene radical from thesilicon atom to which it is bonded. This invention also encompassessilyl acyl peroxides in which the silicon atom is bonded to hydrolyzablefunctional radicals such as halide, alkoxy, aroxy, acyloxy and the like.

This invention also relates to copolymers produced by thecopolymerization of the aforesaid silyl acyl peroxides with one or moreethylenically unsaturated monomers and encompasses copolymers of the ABAblock copolymer type wherein A is the repeating units resulting from theethylenically unsaturated monomer and B is a polysiloxane chain.

Previous efforts have been made in the art to produce silicon compoundscontaining peroxide functions bonded to silicon through a carbon tosilicon bond. Though there have been successes in producing suchcompounds containing the peroxide function, the resulting compoundpossessed little more utility than a conventional wholly organicperoxide, and had the additional disadvantage of costing substantiallymore to produce. The fault with such previous efforts lies in the factthat these silicon compounds were devoid of the hydrolyzable andcondensable functionality bonded directly to silicon which was provenimportant in silicone chemistry in creating desirable silicon polymersof either resinous, oily or rubbery properties. In order to incorporatethe peroxide function into a silicone structure, the prior art requiredincorporation of the peroxide function into special silicone polymers oflimited structures, and these were devoid of residual hydrolyzable andcondensable functionality. As a result, the prior art has produced suchcompounds either as non-hydrolyzable silanes or as oily, fully condensedsilicone polymers.

For example, U.S. Pat. No. 2,963,501 discloses certain fully-condensedorgano silylhydroperoxides. These hydroperoxides were formed by thereaction of the corresponding organosilicon alcohol with hydrogenperoxide in the presence of sulfuric acid. This strong acid reactionwould of course attack any hydrolyzable functional groups, if they werepresent, and therefore none are present.

This same patent discloses a second reaction in which the aforedescribedfully-condensed organo silyl hydroperoxides are reacted with ahydrocarbon acyl chloride in the presence ofa hydrogen halide acceptor,such as pyridine, to form a corresponding organo silyl peroxide having aterminal hydrocarbon acyl radical and co-product HCl. The product thusformed is not the compound of this invention. Firstly, there are nohydrolyzable functional groups bonded to the silicon nor could therelogically be such reactive groups in that disclosure for reasonsdiscussed. Secondly, the acyl carbonyl structure is terminally added tothe silyl peroxy structure in that patent whereas this inventiondiscloses a silyl acyl peroxy structure wherein the acyl carbonylstructure is bonded both to the organo silyl structure and to the peroxystructure. Thus the diacyl silyl peroxy compounds useful inpolymerization initiation of monomers having olefinic unsaturation canbe produced and are also a part of this invention. But a diacyl silylstructure could not be formed by the disclosure of U.S. Pat. No.2,963,501 because of single terminus acyl carbonyl substitution reactiondisclosed therein.

The silyl acyl peroxides of this invention in the form of silanes havinghydrolyzable functional radicals have a distinct advantage over theprior art when these silanes are employed as coupling agents, insofar asthese silanes, through hydrolysis and condensation tenaciously bond theresulting siloxane to inorganic oxide substrates to allow the peroxyfunctionality react with an organic substrate supplied in contact withthe inorganic oxide.

The organosilyl peroxides of U.S. Pat. No. 2,963,501 are disclosed asbeing useful in vulcanizing rubbers but cannot bond inorganic substratesto organic substrates in the manner afore-described.

Further the silyl acyl peroxides of this invention when used asinitiators for the polymerization of olefins offer a distinct advantageover prior art peroxy initiators in that the resulting olefin polymersthrough coreaction with the silyl acyl peroxides contain silylhydrolyzable functional end groups capable of further bond formation.

This invention relates to silyl acyl peroxy compounds containing atleast one of the following structures;

H O I l R N y 00R" and wherein w is l to 3 inclusive; y is 0 or 1, and zis l or 2; with the proviso that when y is 0, the acyl carbonyl carbonis bonded to R, the R having at least 2 sequential carbon atomsseparating the acyl carbon atom from the silicon atom; with the furtherproviso that when y is 1, z is l and the nitrogen atom is bonded to R,the R having at least 3 sequential carbon atoms separating the nitrogenfrom the silicon atom.

wherein Z is Z or Illustrative of the classes of acyl peroxides silanesincluded in this invention are;

'0 i 0 0 4 t t t t ZQSIR'NH 00R, ZgSlR' 00R and ZaSlR' 00 R'SlLg whereinR, R" and Z are hereinbefore defined.

This invention also relates to silyl acyl peroxy compounds, asaforesaid, wherein said compounds are acyl peroxy polysiloxanes.

It is well known in the art that halosilanes, alkoxysilanes,aroxysilanes, acyloxysilanes, aminosilanes and hydrosilanes can behydrolyzed to form silanols, silanetriols, depending upon their degreeof hydrolyzable functionality. These silanols can be condensed orco-condensed to form networks of siloxane chains. Generally, undernormal commercial usage, the silanediols and triols are unstabletransitory materials and readily condense to siloxane; and exist, whenthey do exist, only in water. Cross-linking of siloxane chains, byestablishing Si-O-Si bridges across the siloxane chains, occurs when oneof the silanols contains at least three functional groups. In thesereactions the composition of the final product is controlled by suitableproportioning of the hydrolyzable silanes and the organoradicals/silicon ratio in the mixture of intermediates beingsubstantially the same as that in the product.

It is within the contemplation of this invention to form multitudinoussiloxane copolymers by the co-condensation of the intermediates of thefunction silyl acyl peroxides, pursuant to this invention, with othersilane intermediates.

By selection of functional silanes, polysiloxanes of a wide range ofmolecular weights can be formed and any degree of polymerization isobtainable from oils to gums to resins.

By way of example, the following more specific acyl peroxy polysiloxanesare within the contemplation of this invention;

o ROO& N R'(R2SiO) RzSiR(l I) COOR" (I) wherein R is an alkyl radical offrom about one to l2 carbon atoms and a is any number from about 2 to200, and wherein R, R and y are hereinbefore defined;

wherein m is a number from about to 200 and wherein polymer ll terminalend-blocking groups are monovalent organic radicals resulting from theformation of II and wherein R, R", R, y and a are hereinbefore defined.

proposed theory, initiation of the copolymerization is believed to occurby thermal degradation of the acyl peroxide,

H E (N) OOR to form the free radicals or degradation of the diacylperoxide,

to form free radicals,

The ethylenic-peroxy copolymerization is carried out in an inert gasenvironment, such as argon, neon or xenon. The temperature of thereaction is important insofar as being sufficiently high to thermallydegrade the peroxy bond and yet sufficiently low to prevent otherundesirable reactions. Reaction temperatures generally range from about60C. to 250C. and reaction periods generally from about 1 to 10 hours.

Essentially all monomers having ethylenic unsaturation capable ofpolymerization are suitable for use pursuant to this invention.Illustrative of such ethylenically unsaturated monomers include thealkenes such as ethylenes as propene, butene, octene, decene and thelike, preferably the alkenes having terminal carboncarbon unsaturationsuch as propene, l-octene, ldecene and the like; the aryl alkenes,preferably styrene, a-methylstyrene, and the like; the vinyl esters suchas vinyl acetate, vinyl propionate; acrylic monomers such as acrylicacid, methyl methacrylate, methylacrylate, 2-ethyl-n-hexyl-acrylate,acrylamide, acrylonitrile and the like: divinyl phenyls such as divinylbenzene and the like; vinyl naphthyls; alkadienes, such as1,3-butadiene; isoprene, chloroprene, and the like; vinyl halides suchas vinyl chloride, vinyl fluoride and the like; vinylidene halides suchas vinylidene bromide, vinylidene flouridevinylidene chloride and thelike.

The silyl acyl peroxides of this invention can be prepared by theaddition reaction, in the presence of a catalyst, of a compound havingsilanic hydrogen with an acyl peroxide having carbon-carbonunsaturation. Preferably the unsaturation is terminal carbon-carbonunsaturation. This reaction is carried out at moderate temperatures ofabout 25C. for periods up to hours or more, if required and isillustrated as follows;

wherein R, R" and Z are as hereinbefore defined, R is a divalenthydrocarbon such as alkylene, alkarylene, alkarylalkyiene or arylenehaving 2 less sequential carbon atoms than R.

The silyl carbamyl peroxides of this invention, can be prepared by thereaction of an silylorgano isocyanate with an alkyl hydroperoxide atmoderate temperatures of about 25C., to 100C., for periods up to about25 hours or more, in the presence of a catalyst, as follows;

wherein R, R" and Z are hereinbefore defined.

The disilyl diacyl peroxides of this invention can be prepared by theaddition reaction, under reaction conditions similar to those for themonosilyl acyl peroxides, of a compound containing silanic hydrogen witha poly-unsaturated diacyl peroxide. Preferably the unsaturation is inthe terminal positions, as shown as follows;

0 0 zasiR'ilooiin'siza wherein R, R, and Z, are as hereinbefore defined.

The above reactions may be carried out in the presence or absence of asolvent which is inert to the functional groups, -N=C=O, -OOH, or=SiI-I. Examples of such solvents are aliphatic hydrocarbons such ashexane or heptane, cycloaliphatic hydrocarbons such as cyclohexane,aromatic hydrocarbons, such as benzene or toluene. Preferably thereaction is carried out in the presence of a solvent. The operatingtemperature is not critical in the above reactions, but it isadvantageously operated between about 25C. and about 100C. Preferablythe reaction is carried out at temperatures near 25C. for periods up toabout I00v hours or more. The catalysts employed for the additionreaction of the unsaturated acyl peroxide to Si-H are preferablyderivatives of group VIII metals, such as ruthenium or platinumderivatives, for example bis(4- chlorobenzonitrile) dichloroplatinum(II) and 1,3- distyrene-2,4-dichloro-u-dichloroplatinum (II). In theisocyanate-hydroperoxide reaction the catalysts employed are preferablyderivatives of the higher group IV metals, preferably tin (II), forexample stannous 0ctoate, but may also be organoamines such astriethylamine and the like.

The polymers as represented by general formulas I and II can beprepared, under the reaction conditions of the hereinbefore describedmonomer syntheses, with polyfunctional reactions, as follows;

wherein R, R, R and m, are as hereinbefore defined, and

followed by,

(IV) HOOR" Iwoo NnRaRzsio) RzsiR Nfiil00R" (I) wherein R, R, R, R and a,are as hereinbefore defined and wherein the reaction of the intermediateisocyanate (IV) with the hydroperoxide is carried out in the presence ofa catalyst, preferably of the class R N, wherein R is hereinbeforedefined, and a preferred catalyst is triethylamine, at temperatures from25C. to C.

It is understood that in the afore-described monoolefin and polysiloxanereactions, an active hydrogen of the polysiloxane may alternatively belocated along the polymer chain in contradistinction to a terminalposition, in which case the resultant polymer chain will contain pendantsilyl acyl peroxy or silyl carbamyl peroxy radicals.

In the above polymer syntheses R is preferably methyl and R" ispreferably cumyl or tertiary-butyl.

Illustrative of hydroperoxides suitable in the aforesaidisocyanate-hydroperoxide reactions are the following: methylhydroperoxide, ethyl hydroperoxide, propyl hydroperoxide, isopropylhydroperoxide, nbutyl hydroperoxide, sec-butyl hydroperoxide, t-butylhydroperoxide, t-amyl hydroperoxide, l,l-diethylpropyl hydroperoxide,l,l ,Z-trimethylpropyl hydroperoxide, lmethylhexyl hydroperoxide,l,l,2,2- tetra methylpropyl hydroperoxide, cyclohexyl hydroperoxide,4-methylcyclohexyl hydroperoxide, and the like.

For the purposes of this invention R can be any alkylene, or aralkyleneor alkarylakylene group. Generally R will have from 2 or 3 (ify is O) tol2 carbon atoms but need not be so limited. Illustrative of R arealkylene (such as methylene, ethylene, n-hexylene, Z-ethyI-n-hexylene,and the like); arylalkylene (such as phenylethylene, and the like);cycloalkylene (such as l,4-cyclohexylene, l,3-cyclohexylene,1,3-cyclobutylene, and the like), and the like.

For the purpose of the invention R can be any alkyl or aralkyl group.Generally R will have from I to 12 carbon atoms but need not be solimited. Illustrative of R are alkyl (such as methyl, ethyl, pentyl,dodecyl, octadecyl, 2-ethylhexyl, and the like); cycloalkyl(such ascyclobutyl, cyclohexyl, 4-methylcyclohexyl, and the like), aralkyl (suchas phenylethyl, cumyl, and the like), and the like.

For the purposes of this invention Z can be a hydrolyzable functionalradical such as halide (such as chloride, bromide and fluoride); alkoxy(such as methoxy, ethoxy, propoxy, n-dodecyloxy, isopropoxy,2-chloroethoxy, 2-chloroisopropoxy, and the like); acetoxy, (propioroxy,and the like); amino; alkylamino and arylamino (such as methyl amino,diemthylamino, diethyl amino, phenyl amino, and the like); hydroxyalkoxy (such as beta-hydroxyethoxy, gammahydropropoxy, and the like);hydroxyalkoxyalkoxy (such as beta-hydroxyethoxy-ethoxy, omega-hydroxy-(polethyleneoxy)ethoxy, omega-hydroxy-(poly-l ,2,- propyleneoxy);oximido; and the like. Z can additionally and alternatively be amonovalent organic hydrocarbon radical, such as generally of from I to 8linear sequential carbon atoms but not necessarily so limited.Illustrative of such monovalent organic radicals are alkyl (e.g.,methyl, ethyl, pentyl, octadecyl, 2- ethylhexyl, and the like),cycloalkyl (such as cyclobutyl, cyclohexyl, 4-methylcyclohexyl, and thelike), aryl (such as phenyl, Z-napththyl, Z-anthracyl, biphenyl, and thelike), alkaryl (such as 4-methylphenyl, 2,4- diethylphenyl,4-dodecylphenyl, and the like), aralkyl (such as phenylethyl), alkenyl(such as vinyl, allyl, 3- butadenyl, oleyl, and the like), alkadienyl(such as lbutadienyl-l,4,l-octadecatrienyl-9, l 1, l3, l-neoprenyl, andthe like, cycloalkenyl (such as 3-cyclohexenyl), haloalkyl (such aschloromethyl, gammachloropropyl, 3,3,3-trifluoropropyl,perfluoropropyl), haloaryl (such as 4-chlorophenyl, 2,4-dichlorophenyl,chloronapthyl), halocycloalkyl (such as 4chlorophenyl), cyanoalkyl (suchas beta-cyanoethyl, gammacyanopropyl, and the like); cyanoaryl (such as4- cyanophenyl); cyanocycloalkyl (such as4-cyanocyclohexyl,3-cyanocyclopentyl, and the like); carboxyalkyl (suchas beta-carboxyethyl, gamma-carboxypropyl, and the like); carboxyaryl(such as 4-carboxycyclohexyl, 3-carboxycyclopentyl; and the like);isocyanatoalkyl (such as gamma-isocyanatopropyl, deltaisocyanatobutyl,and the like); isocyanatoaryl (such as 4-isocyanatophenyl);isocyanato-cycloalkyl (such as 4isocyanatocyclohexyl); alkyl or arylcarboxalkyl (such as beta-methylcarboxyethyl, gamma-phenyl carboxypropyl, and the like), and the like.

The silyl acyl peroxy compounds of this invention can be used for any ofthe purposes for which peroxides are generally employed, such asinitiators for the polymerization of olefins and as vulcanizing agentsfor rubbers. For example the hydrolyzable functional silyl acylperoxides can be used as initiators for the polymerizationof monomershaving olefin unsaturation such as styrene or methylmethacylate, inwhich cases the resulting polymer contains hydrolyzable functional silylacyl end groups. It is understood that these end groups are desirable informing bonds to polar substrates such as siliceous substrates.

The polyfunctional silyl acyl peroxy compounds of this invention canalso be used as -coupling agents and binders for polymers, rubbers,metal oxide, siliceous and metallic substrates.

Illustrative of substrates within the purview of this invention are, byway of example, metal substrates, such as aluminum, iron, copper, steel(stainless steel, carbon steel, and the like), magnesium titaniumzirconium, nickel, stainless steel alloys, chromium steel alloys,chromium plate, copper, zinc, bronze, brass, gold, platinum, silver,iridium, and the like; metal oxide substrates, such as aluminum oxide,titanium oxide; titanium oxides, lead oxides, copper oxides, ironoxides, beryllium oxides, manganese oxides, tungsten oxides,

tantalum oxides, vandium oxides, and the like; nonmetal inorganicoxides, such as silicon oxides (e.g., sand, fly ash, hydrated silica,silica, quartz, aerogels, xerogels, fumed silica, and the like);aluminum silicates (such as clay, asbestos, and the like); glass, inessentially any form (e.g., fiber, plate, granular, spheres, and thelike), other inorganic solid salts, such as calcium carbonate, magnesiumcarbonate, magnesium sulfate, lead chromate, iron chromates; as well ascarbonaceous inorganic materials, such as graphite in essentially anyform, carbon black; boron nitride;

polyaminoboranes; polyphosphinoaminoboranes; and the like.

The polymer substrates may be of solid, natural or synthetic organicmaterial, such as cellulosics, e.g., wood (in any shape, e.g., as woodflour, paper, boards, composites, and the like); cotton, rayon,cellulose acetate, cellulose triacetate, nitrocellulose, and the like,in any form, e.g., particulate, film or fiber; polyamides, such as wool,silk, zein, horse hair, hogs hair, human hair, leather,poly)hexamethyleneadipamide )poly-epsilon-caprolactam, polypryrrolidone;polyesters such as alkyd resins, polymerized linseed oil, oxidizedlinseed oil and other drying oils, bodied natural oils which aretriglycerides of fatty acids, polyethyleneterephthalate,polycyclohexyleneterephthalate, poly-epsilon-caprolacton and the like;organic rubbers, such as natural rubber, such as 1,3-butadiene-styrenecopolymers, polysulfide rubbers, ethylacrylate polymers, poly-l3-butadiene, poly-l-butene, polyurethane spandex polymers such as apolyester of adipic acid and 1,4-butane diol which is terminated byreaction with bis(4-isocyanatophenyl)methane and this isocyanatoprepolymer is chain extended with l,4-butane diol, or a polyester ofpoly-epsiloncaprolactone initiated by reaction with diethylene glycoloptionally followed by reaction with toluene isocyanate (i.e., mixedisomers of the 2,4- and 2,6-varieties), which prepolymer is capped byreaction with bis(4-isocyanatophenyl) methane and this prepolymer ischain extended with ethylene diamine, or the same type of spandexpolymer except that for the caprolactone polyester there is employed apolyether diol, such as poly (oxytetramethylene)glycol and in such casesthe same extension may be effected with hydrazine instead of ethylenediamine; copolymers of ethylene and/or propylene and a polyolefin suchas, e.g., l,3-butadiene, 2-ethyldienenorbornene-5 (or 6) and the like;silicone rubbers, such as poly(dimethylsilyloxy) (commonly referred toas dimethylpolysiloxane), copolymers of such siloxane containingvinylsilyl groups and the like; polyolefin resins, such as homopolymersand copolymers of ethylene, propylene, l-butylene, vinylacetate, vinylformate, vinyl propionate, vinyl chloride, N-vinyl pyrrolidone,acrylonitrile, styrene, butadiene-l,3 maleic acid, fumaric acid, acrylicacid, methacrylic acid, crotonic acid, alkyl and aryl esters of theaforementioned acid, tetrafluoroethylene, trichlorofluoroethylene, vinylsilanes, and the like; polyaryl ethers and polyarylsufones andcopolymers of the two; silicone resins, epoxy resins such as thecycloaliphatic epoxides or themematic epoxides, the latter typicallybeing based on the glycidyl ethers of bis phenol A; phenol-foraldehyderesins, melamine-formaldehyde resins, melamine-formaldehyde resins;unreaformaldehyde resins; polycarbonates based on the bis phenol Acarbonates or the aliphatic polycarbonates; and the like. Essentiallyany polymer, rubber, siliceous, metallic or the like substrates may bebonded to each other or themselves utilizing the silyl acyl peroxycompounds of this inventlon.

Bonding may be effected in a number of ways. For example, the silyl acylperoxide can be incorporated into a liquid version of the material whichis to result in the formation of a solid surface which adheres toanother solid surface or which can be coated on either one or both ofthe surfaces being-joined. One may bond glass to glass or aluminum toaluminum or aluminum to essestially any organic resin or polymers justwith a solvent solution of the silyl acyl peroxide, provided in eachcase there is sufficient intimate contact between the surfaces. In everycase, the silyl acyl peroxide will act to enhance adhesion when comparedto such attempts to adhere absent a bonding aid and simply involvingcommon contact between the materials. Of course, thermosetting orthermoplastic materials can be joined, provided they are compatible,with heat alone, absent the silyl acyl peroxide. But it must beremembered that when such materials are so joined they must typically bein a common plastic state to obtain optimum adhesion, whereas when'oneemploys the silyl acyl peroxide of this invention in either one of thematerials, it is not necessary to employ temperatures which will liquifythe material, interfacial softening is all that is needed. Thus, one maytake two incompatible thermosetting plastics, and provided one makesintimate contact between them and silyl acyl peroxide is provided at theinterface, then enhanced bonding or adhesion of the two articles willresult.

The following examples are illustrative only and should not be construedin any way so as to limit the invention.

In the following examples, iodometric analyses to measure the activeoxygen content of the product silyl acyl peroxides, to determine purity,were performed accordingly to the method of C1. Pederson, as presentedin 23 J.Org.Chem., 252( l958) and said analytical procedure isincorporated herein by reference.

EXAMPLE I A solution was prepared by manually adding 30.7 grams oftert-butyl hydroperoxide to 220 grams of benzene. The aforesaid solutionwas added dropwise during a period of 50 minutes at room temperature toa mixtue consisting of 70 grams of 3-(trimethoxysilyl)propyl isocyanate,1.0 gram of stannous octoate and 220 grams of benzene. After additionwas complete the resultant reactant mixture was mechanically stirred fora total of 2 hours. The reaction exotherm produced a temperature of 36C.Upon completion of the 2 hour reaction period an infraredspectrophotometric analysis could not detect the presence of3-(trimechoxysilyhpropyl isocyanate. The benzene was removed by drawinga vacuum of lOOmmHg for 60 minutes while the reaction vessel was heatedand maintained at 40C. The resulting reaction product was 100.8 gramsoftert-butyl N-[3(trimethoxy silyl)-propyl] peroxy carbamate of 96.6percent purity as determined by the method of Pederson. This productvalue represented a 96.7 percent yield.

EXAMPLE 2 a reaction charge was prepared by mixing 70 grams ofS-(trimethoxysilyl) propylisocyanate, 62.1 grams of cur'nenehydroperoxide of 83.6 percent purity, 1.3 grams of stannous octoate and700 grams of benzene. The reaction charge was heated to 80C. andmaintained at that temperature for 4 hours during which period thereaction charge was continuously mechanically stirred. Upon completionof the 4 hour reaction period an infrared spectrophotometric analysiscould not detect the presence of H 3 (trimethoxysilyl)propylisocyanate.The benzene was-removed by drawing a vacuum of 400 mm Hg for,60 minuteswhile maintaining the reaction mixtureat 55.65C-. The resulting reactionproduct was l32-grams of cumyl N- [3(trimethoxysilyl)propyl]peroxycarbamate of 75.1 percent purity as determined by the method ofPederson. This product value represents 78.6 percent yield oftheoretical.

EXAMPLE 3 A reaction charge was prepared by mixing 2.4 grams oftrimethoxysilane, 5.0 grams of tert-butyl peroxyl O- undecenoate, 0.005gram of bis(4- chlorobenzonitrile)dichloroplatinum (ll) and 22 grams ofbenzene. The reaction charge was allowed to stand at 25C for 40 hours.Upon completion of the 40 hour period infrared spectrophotometricanalysis detected only traces of silanic hydrogen. The resultingreaction product was 6.8 grams of tert-butyl-ll-(trimethoxysilyl)peroxyundecanoate of 95.0 percent purity asdetermined by the Pederson analytic method. This product valuerepresented an 87.3 percent yield of theoretical.

EXAMPLE 4 A reaction charge was prepared by mixing 2.70 grams oftrichlorosilane, 5.00 grams of tert-butyl-lO- undecenoate, 0.005 gramsof bis(4- chlorobenzonitrile)dichloroplatinum (I1) and 22 grams ofbenzene. The reaction mixture was allowed to stand at 25C. for 22 hours.Then an additional 0.005 grams ofbis(4-chlorobenzonitrile)dichloroplatinum (II) was added. The reactionmixture was allowed to remain at 25C. for an additional 72 hours. Thebenzene was removed by drawing a vacuum of mm Hg for 60 minutes atambient temperature.

The product yield was 7.2 grams of tert-butyl-l ltrichlorosilyl) peroxyundecanoate with a purity of 83.3 percent as determined by the Pedersonanalytical method. This product value represents a product yield of 77.9percent of theoretical.

EXAMPLE 5 A reaction charge was prepared by mixing 24.7 grams oftrimethoxysilane, 36.9 grams of bis(l0-undecenoyl)peroxide, which wasprepared by reacting IO-undecenoyl chloride with sodium peroxide, 0.022grams of bis(4-chlorobenzonitrile) dichloroplatinum (ll) and 132 gramsof benzene. The benzene was removed by drawing a vacuum of 100 mm Hg for60 minutes at 25C. The reaction charge was transferred to a Servall SS-3centrifuge having an SS-34 rotor and subjected to a centrifugal force at5000 revolution per minute (rpm) for 30 minutes to separate out theproduct.

The product yield was 54.0 grams of bis[l1- (trimethoxysilyl)undecanoyl] peroxide of 83.0 percent purity, as determined by thePederson analytical method, which yield represented 72.8 percent oftheoretical.

EXAMPLEo A reaction charge was prepared by mixing 2.2 grams oftrichlorosilane, 3.0 grams of bis( l-undecenoyl) peroxide, 0.00024 gramsof 1,3-distyrene-2, 4- dichloro-u-dichloro-diplatinum (II) and 13.7grams of toluene. The charge was allowed to stand at 25C. for 24 hours,during which additional platinum compound in the total amount of 0.0015part was charged in several increments. The charge was allowed to standfor an additional 90 hours after the last platinum addition.Spectrophotometric analysis indicated only traces of silanic hydrogen.The toluene was removed in vacuo of 20 mm Hg for 60 minutes, at ambienttemperature. The yield was 5.0 grams, bis[ 1 l-(trichlorosilyl)undecanoyll peroxide. Pederson analysis indicated apurity of 92.5 percent which represented a yield of 89.0 percent oftheoretical.

EXAMPLE 7 A reaction charge was prepared by mixing 100 grams ofpolysiloxane having the formula HMe SiO)Me SiO), SiMe H, 4.52 grams of9-decenyl isocyanate and 0002 grams ofl,3-distyrene-2,4-dichloro-adichlorodiplatinurn (ll). The charge reactedcausing a temperature rise 6C. above the ambient temperature (25C.).Infrared spectrophotometric analysis indicated that terminal silanichydrogen of the polysiloxane was consumed within 13 minutes. After 55minutes. the charge was evacuated at mm Hg 150C. for 45 minutes.Infrared analysis indicated the presence of isocyanate groups, but noSiH groups. Cumene hydroper oxid e, 3.5 grams, (83 percent purity) and0.094 grams of triethylamine were added to the charge. The mixture wasthen heated to 80C. and maintained at that temperature for 2 hours. Thecharge was evacuated by drawing a 0.5 mm Hg vacuum for about 45 minutes.The Pederson analytical method was used to indicate a number averagemolecular weight of 13,900 for the peroxide-endblocked polysiloxane.

EXAMPLE 8 A reaction charge was prepared by mixing 50 grams of thepolysiloxane HMe SiO(Me SiO) SiMe l-l, 7.5 parts of bis(l0-undecenoyl)peroxide and 8.7 grams of a toluene solution containing0.003 gram of 1,3- distyrene-2,4 dichlorot-dichloro-diplatinum (ll). Thecharge allowed to stand at 25C. for about 43 hours. At the end of thisreaction period, silanic hydrogen could not be detected by infraredspectrophotometry. The toluene'was removed in vacuo at 20 mm Hg for 60minutes at ambient temperature. Pederson analysis indicated retention of85.2 percent of the active oxygen in the l0-undecenyl peroxy end-blockedpolysiloxane product.

EXAMPLE 9 A reaction charge was prepared by mixing 10.0 grams of theperoxy end-blocked polysiloxane as prepared in Example 9 with 30.0 gramsof inhibitorfree styrene and 86 grams of xylene. The charge was heatedfor 6 hours at 120C. in an argon atmosphere. The charge became turbidand separated into two phases on standing. Evaporation of the solventfrom the upper phase yielded a nearly clear, soft, rubbery polymer.Elemental analysis indicated that the polymer contained 64.2 percentpolysiloxane by weight bond on the weight of the polymer. This wouldindicate a copolymer number average molecular weight of 21,600 since themolecular weight of the polysiloxane block is 13.900. The polystyrenecontributed the balance, that is 7,700. The average molecular weight ofthe polystyrene blocks, therefore, would be about 3,850, since there aretwo blocks per molecule.

EXAMPLE '1 0 A series of five test tubes was sparged with argon and Icharged with inhibitor-free styrene and with theperoxyorganopolysiloxane of Example 10. Total charge was 5.0 gramincrements (that is a range of 40-80 weight percent based on the weightof the charge). The tubes were heated in a water bath at 9l-94C. for 6hours. Each sample was dissolved in about 26 parts of benzene,precipitated in 790 parts of methanol and dried. The results are shownbelow in Table 1;

A glass ampoule was charged with 25 grams of inhibitor-free styrene and0.25 grams of cumyl N-[3- trimethoxysily1)propyl] peroxycarbamate (asprepared in Example 2). The charge was frozen in liquid nitrogen andevacuated at 1.0 mm Hg for 15 minutes. The ampoule was then filled withargon and the contents were allowed to melt. The solid-liquid transitioncycle was repeated twice. The ampoule was sealed and immersed in an oilbath at C for 16 hours, during which the charge polymerized to a yellowsolid. The solid was dissolved in 350 grams of benzene and was filteredthrough No. 3 paper. It was precipitated by dropwise addition to 3200parts of stirred methanol. The product was collected on a No. 3 filterpaper and dried. Silicon content of the product was 0.066 weightpercent. This corresponds to a number average molecular weight of about22,000.

Benzene solutions containing 4 weight percent of the experimentalpolymer is prepared above and, as a control, of commercial polystyrenewere prepared. Films were cast on glass plates and allowed to evaporate.The plates were heated in an oven for one hour at l40 C. The commercialpolymer was released from the plate within one minute after immersion inwater at about 25C. The prepared experimental polymer remained bound tothe glass even after a 21 hour immersion at 25C.

EXAMPLE 12 A test tube was sparged with argon and charged with 10.2grams of methyl methacrylate (distilled, b.p. 53C. at 133 mm Hg) and0.127 grams of bis[ 1 l-(trimethoxysilyl)undecanoyl] peroxide. The tubewas heated in a water bath at 70C. The temperature was increased to 83C.The charge became viscous within 24 minutes (at 83C.) and solid within43 minutes (at 83C.).

Heat was maintained for a total of 3 hours. The resultant polymer wasdissolved in chloroform and precipitated in petroleum ether. Theprecipitate was separated by filtration, washed with pentane and dried,yielding 8.5 parts of a fluffy white solid. Analysis indicated 0.12weight percent silicon. The number average molecular weight was 23,400(assuming one silicon atom per molecule).

A film which was cast on glass from chloroform solu tion and oven-driedat 140C. for about 20 minutes to form a bond which was resistant towater immersion at 25C. for an indefinite period.

EXAMPLE 13 Cumyl N-[3-(trimethoxysilyl)propyllperoxycarbamate (asprepared in Example 2) was applied as a 0.5 weight percent methanolsolution on 181-1 12 glass fabric. A dry laminate of alternating pliesof 12 sheets of 10 mil polypropylene and 11 sheets of glass cloth wasprepared and placed in a platen press preheated to 400F. The laminatewas compared to 0.125 inch heat and pressure was maintained for 30minutes. The press was then cooled to amient temperature and thelaminateremoved. The resultant laminate had a nominal thickness of 0.125inch and contained 4012 weight percent polypropylene based on the weightof laminates. Specimens were cut to 4 inches by V: inch rectangles, withthe long dimension along the warp of the fabric. Flexural strengths weredetermined according to ASTM D790-63. Tests were conducted on drysamples both at room temperature and at 200F. Tests were also conductedat room temperature on samples that had been soaked in distilled waterfor 16 hours at 120F. Tests were also conducted on control samplesprepared from untreated glass fabric. The results are listed in Table11.

TABLE [1 Flexural Strength (psi.)

Room Temperature 200F. Water-Soaked Control l3,(l 4,800 10,000 Test 23.000 14,000 20,000 Sample EXA M PLE l 4 Aluminum, brass and steel stripswere wiped clean with methanol and allowed to dry. Strips of curedsilicone rubber were treated in the same manner. Each surface was coatedwith solution containing parts of tert-butyl N-[3-(trimethoxysilyl)propyllperoxycarbamate (s'ee Example 1) in 100 parts by volume of a 2-propanol solution which contained 2 parts by volume of added water. Thecoatings were air-dried. The rubber and metal were joined and heated ina platen press at 360F. and about 770 psi. for minutes. The

specimens were then removed, cooled and checked for adhesion by peelstrength testing. Cohesive failure was obtained with all three metals.

EXAMPLE 15 Aluminum, steel and glass plaques were painted with a toluenesolution containing 5 weight percent tert-butylN-[3-trimethoxysilyl)propyl]peroxycarbamate. The painted plaques allowedto dry. The coated samples were then contacted with 1/16 inchpolyethylene flat stock in a press at 2500 psi. and 400F. for 10minutes. A bond was formed with all three substrates. The steel andaluminum retained a bond after a 24 hour immersion in water at roomtemperature. A

EXAMPLE 16 Aluminum, steel and glass plaques were painted with a toluenesolution containing 5 weight percent cumylN-[3-(trimethoxysilyl)propyllperoxycarbamate and allowed to dry. Thecoated samples were then contacted with 1/16 inch polyethylene flatstock ina press at 2500 psi. and 400F. for 10 minutes. A bond was formedto all three substrates. The glass and the aluminum retained a bondafter a 24 hour immersion in water at room temperature.

What is claimed is:

l. A copolymer of a) a polysiloxane of a silyl acylperoxy compoundcontaining at least one of the following structures;

wherein Z, R, R and y are as herein defined and w is 1 to 3 inclusive; yis 0 to 1, and z is l or 2; with the proviso that when y is 0, the acylcarbonyl carbon is bonded to R, the R having at least 2 sequentialcarbon atoms separating the acyl carbonyl carbon atom from the siliconatom; with the further proviso that when y is 1, z is 1 and the nitrogenatom is bonded to a carbon wherein Z is Z or atom of R, the R having atleast 3 sequential carbon atoms separating the nitrogen from the siliconatom, and b) an ethylenically unsaturated monomer.

2. The copolymer of claim 1 wherein the polysiloxane has the generalformula:

wherein R is alkyl radical of from about one to twelve carbon atoms anda is a number from about 2 to 500.

3. The copolymer of claim 1 wherein the polysiloxane has the generalformula:

L B J") wherein R is an alkyl radical of from about one to twelve carbonatoms, m is a number from about m 200, a is a number from 2 to 500 andthe terminal endblocking groups are resultant monovalent organicradicals from the formation of said polysiloxane.

4. The copolymer of claim 2 wherein said ethylenically unsaturatedmonomer is a vinyl ester.

5. The copolymer of claim 2 wherein said ethylenically unsaturatedmonomer is an alkene.

6. The copolymer of claim 5 wherein said ethylenically unsaturatedmonomer is an aryl alkene.

7. The copolymer of claim 6 wherein said ethylenically unsaturatedmonomer is styrene.

8 The copolymer of claim 2 wherein said ethylenically unsaturatedmonomer is methyl methacrylate.

9. The copolymer of claim 1 wherein the copolymer is an ABA copolymerwherein A is a repeating unit resulting from polymerization of theethylenically unsaturated monomer and B is the polysiloxane.

10. A method for polymerization of an ethylenically unsaturated monomerwhich comprises heating in a reaction environment such monomer in thepresence of an initiator which is a silyl acylperoxy compound containingat least one of the following structures;

wherein R is an alkylene, aralkylene or alkarylalkylene radical, R is analkyl or aralkyl radical, Z is a monovalent hydrolyzable radical ormonovalent organic radical bonded to the silicon atom by a carbon tosilicon bond and wherein x is an integer from O to 3 inclusive, andprovided that when x is greater than zero, the oxygen atom is in turnbonded to another silicon whereby to form a siloxane, wherein saidsiloxane and any remaining siloxane units in said siloxane compositionare of the formula;

atom of R, the R having at least 3 sequential carbon atoms separatingthe nitrogen from the silicon atom" and the reaction environment is nertto sm polymerization.

2. The copolymer of claim 1 wherein the polysiloxane has the generalformula:
 3. The copolymer of claim 1 wherein the polysiloxane has thegeneral formula:
 4. The copolymer of claim 2 wherein said ethylenicallyunsaturated monomer is a vinyl ester.
 5. The copolymer of claim 2wherein said ethylenically unsaturated monomer is an alkene.
 6. Thecopolymer of claim 5 wherein said ethylenically unsaturated monomer isan aryl alkene.
 7. The copolymer of claim 6 wherein said ethylenicallyunsaturated monomer is styrene.
 8. The copolymer of claim 2 wherein saidethylenically unsaturated monomer is methyl methacrylate.
 9. Thecopolymer of claim 1 wherein the copolymer is an ABA copolymer wherein Ais a repeating unit resulting from polymerization of the ethylenicallyunsaturated monomer and B is the polysiloxane.
 10. A method forpolymerization of an ethylenically unsaturated monomer which comprisesheating in a reaction environment such monomer in the presence of aninitiator which is a silyl acylperoxy compound containing at least oneof the following structures;